CN113272384B - Thermoplastic polyurethane compounds exhibiting improved resistance to contamination - Google Patents
Thermoplastic polyurethane compounds exhibiting improved resistance to contamination Download PDFInfo
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- CN113272384B CN113272384B CN202080008301.2A CN202080008301A CN113272384B CN 113272384 B CN113272384 B CN 113272384B CN 202080008301 A CN202080008301 A CN 202080008301A CN 113272384 B CN113272384 B CN 113272384B
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- thermoplastic polyurethane
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- polycaprolactone
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 182
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- 238000012360 testing method Methods 0.000 claims abstract description 17
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- 238000005299 abrasion Methods 0.000 claims abstract description 15
- 230000001681 protective effect Effects 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 21
- 229920001610 polycaprolactone Polymers 0.000 claims description 14
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- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- 229920006132 styrene block copolymer Polymers 0.000 claims description 7
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- 239000003795 chemical substances by application Substances 0.000 claims description 6
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- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 4
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- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 17
- 239000000654 additive Substances 0.000 description 13
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- 239000004970 Chain extender Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920005862 polyol Polymers 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
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- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 2
- UHKPXKGJFOKCGG-UHFFFAOYSA-N 2-methylprop-1-ene;styrene Chemical compound CC(C)=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 UHKPXKGJFOKCGG-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
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- 229920002397 thermoplastic olefin Polymers 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000004262 Ethyl gallate Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
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- 102220490345 S-adenosylhomocysteine hydrolase-like protein 1_S85A_mutation Human genes 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- 238000003672 processing method Methods 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/487—Polyethers containing cyclic groups
- C08G18/4879—Polyethers containing cyclic groups containing aromatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Thermoplastic articles are molded from thermoplastic polyurethane compounds comprising a blend of an aromatic polycaprolactone-type thermoplastic polyurethane and other aromatic thermoplastic polyurethane selected from the group consisting of: aromatic polyester thermoplastic polyurethane, aromatic polyether thermoplastic polyurethane, and combinations thereof. The thermoplastic articles exhibit enhanced stain resistance, as represented by reaching a rating of 2 or higher according to the blue jeans abrasion test, relative to thermoplastic articles molded from thermoplastic polyurethane compounds comprising only aromatic polyester-type thermoplastic polyurethane or aromatic polyether-type thermoplastic, while also having good clarity (i.e., low haze) and other desirable properties. Thermoplastic articles may be particularly suitable for use in protective cases for handheld electronic devices.
Description
Priority statement
The present application claims priority from U.S. provisional application serial No. 62/790,311, attorney docket No. 12019003, filed on 1/9 at 2019, which is incorporated herein by reference in its entirety.
Technical Field
The present invention relates to thermoplastic polyurethane compounds and thermoplastic articles formed therefrom that have improved abrasion and stain resistance, but also have good clarity and other desirable properties.
Background
There is a need for polymeric materials for manufacturing protective cases and other components or accessories for personal electronic devices such as smart phones, tablet computers, and handheld computers.
Protective cases for personal electronic devices often require good aesthetics, such as "look" and "feel" desired by the consumer. For example, some consumers prefer a protective shell appearance that is relatively clear or light or vivid in appearance. In addition, some consumers prefer a protective shell feel that is relatively soft to the touch and that is not tacky or sticky.
Thermoplastic elastomers (TPEs) are polymeric materials that exhibit elasticity while maintaining thermoplasticity and are useful in the manufacture of protective cases for personal electronic devices. TPEs may include Styrenic Block Copolymers (SBC), thermoplastic vulcanizates (TPVs), thermoplastic Polyolefins (TPOs), copolyesters (COPE), thermoplastic Polyurethanes (TPU), copolyamides (COPA), and Olefinic Block Copolymers (OBC). While some TPEs (e.g., conventional TPU) can provide good transparency and other properties required to make protective cases for personal electronic devices, they are still deficient.
For example, protective cases made from conventional TPU suffer from poor abrasion and stain resistance when a user places a personal electronic device in a garment or article of clothing made from jean or other dyed fabric (e.g., a pocket of blue jean). Disadvantageously, the protective shell may be worn by the fabric and soiled by the dye transferred from the fabric. This wear and contamination is particularly problematic when the protective shell is transparent or light or bright in color.
Summary of The Invention
Accordingly, there is a need for thermoplastic polyurethane compounds and thermoplastic articles molded therefrom that have improved abrasion and stain resistance, but also have good clarity and other desirable properties.
One or more aspects of the present invention address the above-described needs.
Surprisingly, it has been found that by selecting a blend of an aromatic polycaprolactone-type thermoplastic polyurethane and other aromatic thermoplastic polyurethane selected from the group consisting of: aromatic polyester thermoplastic polyurethane, aromatic polyether thermoplastic polyurethane, and combinations thereof.
Some aspects of the invention relate to thermoplastic polyurethane compounds comprising a blend of an aromatic polycaprolactone-type thermoplastic polyurethane and other aromatic thermoplastic polyurethane selected from the group consisting of: aromatic polyester thermoplastic polyurethane, aromatic polyether thermoplastic polyurethane, and combinations thereof, wherein about 20 to about 99 parts by weight is an aromatic polycaprolactone thermoplastic polyurethane and about 1 to about 80 parts by weight is other aromatic thermoplastic polyurethane.
Other aspects of the invention relate to thermoplastic articles molded from thermoplastic polyurethane compounds comprising a blend of an aromatic polycaprolactone-type thermoplastic polyurethane and other aromatic thermoplastic polyurethane selected from the group consisting of: aromatic polyester thermoplastic polyurethane, aromatic polyether thermoplastic polyurethane, and combinations thereof.
Other aspects of the invention relate to methods of making thermoplastic articles. The method comprises the following steps: thermoplastic polyurethane compounds as described herein are provided, as well as molding thermoplastic polyurethane compounds into thermoplastic articles.
Other aspects of the invention relate to methods of improving the resistance of thermoplastic articles molded from thermoplastic polyurethane compounds to blue jeans soiling. The method comprises the following steps: blends of aromatic polycaprolactone thermoplastic polyurethane and other aromatic thermoplastic polyurethane selected to provide thermoplastic polyurethane compounds as described herein to form thermoplastic articles described herein are selected from the group consisting of: aromatic polyester thermoplastic polyurethanes, aromatic polyether thermoplastic polyurethanes, and combinations thereof.
The features of the present invention will become apparent with reference to the following embodiments. There are many variations of the features mentioned in the above aspects of the disclosed invention. Additional features may also be incorporated into the above-mentioned aspects of the disclosed invention. These variations and additional features may exist alone or in any combination. For example, the various features discussed below in relation to any one of the aspects of the present invention may be incorporated into any one of the aspects of the present invention alone or in any combination.
Detailed Description
In some embodiments, the present invention relates to thermoplastic polyurethane compounds. In other embodiments, the present invention relates to thermoplastic articles molded from thermoplastic polyurethane compounds. In other embodiments, the present invention relates to methods of making thermoplastic articles. In other embodiments, the present invention relates to a method of improving the resistance of a thermoplastic article molded from a thermoplastic polyurethane compound to blue jeans soiling. The essential and optional features of these and other embodiments of the disclosed invention are described.
As used herein, "aliphatic polycaprolactone thermoplastic polyurethane" refers to a thermoplastic polyurethane that is the reaction product of reactants comprising a polycaprolactone polyol and an aliphatic diisocyanate, and optionally a chain extender.
As used herein, "aliphatic polyester thermoplastic polyurethane" refers to a thermoplastic polyurethane that is the reaction product of reactants including a polyester polyol (other than a polycaprolactone polyol) and an aliphatic diisocyanate, and optionally a chain extender.
As used herein, "aliphatic polyether thermoplastic polyurethane" refers to a thermoplastic polyurethane that is the reaction product of reactants including a polyether polyol and an aliphatic diisocyanate, and optionally a chain extender.
As used herein, "aromatic polycaprolactone thermoplastic polyurethane" refers to a thermoplastic polyurethane that is the reaction product of reactants comprising a polycaprolactone polyol and an aromatic diisocyanate, and optionally a chain extender.
As used herein, "aromatic polyester thermoplastic polyurethane" refers to a thermoplastic polyurethane that is the reaction product of reactants including a polyester polyol (other than a polycaprolactone polyol) and an aromatic diisocyanate, and optionally a chain extender.
As used herein, "aromatic polyether thermoplastic polyurethane" refers to a thermoplastic polyurethane that is the reaction product of reactants including a polyether polyol and an aromatic diisocyanate, and optionally a chain extender.
As used herein, the term "blue jeans abrasion resistance test" refers to the ford laboratory test method (Ford Laboratory Test Method, FLTM) BN 107-01 abrasion test using the following equipment, settings, materials and conditions:
-instrument: TABER Linear abrader model 5750;
accessory: a tab rubbing color fastness meter attachment with 16mm acrylic fingers;
-abrasive: LEVI' S505 conventionally cuts blue jeans (round cloth cut from the lower part of jeans legs with scissors and placed on the fingers of a crochet machine, the fabric is tilted from the crochet direction and fixed to the fingers with a fixing clip);
length of stroke: 4 inches (100 cm)
-circulation speed: 60 cycles per minute;
load: 9 newtons (918 g); and
-conditions: the temperature was 76°f (24.4 ℃) and the humidity was 47% (and the test specimens were conditioned for at least 24 hours);
-rating: no blue jeans stain/dye after 1 = 100 cycles and 500 cycles; 2=no blue jeans soiling/staining after 100 cycles, but blue jeans soiling/staining occurred after 500 cycles; blue jeans soiling/staining occurred after both 3 = 100 cycles and 500 cycles.
As used herein, the term "blue jeans soiling" refers to the visual observation of discoloration or abrasion due to color transfer on a test specimen (e.g., a thermoplastic article) after the test specimen is subjected to a blue jeans abrasion resistance test.
As used herein, "clarity" refers to a qualitative determination made by visual observation and comparison of a 1.5mm thick sample plate molded from the sample thermoplastic polyurethane compound with a 1.5mm thick control plate molded from pure IROGRAN a 85P 4394UV aliphatic polycaprolactone type thermoplastic polyurethane available from Huntsman corporation. Rating was performed according to the following criteria: 1 = transparency of sample comparable to control; 2 = the sample is blurred relative to the control; 3 = opaque with respect to control.
As used herein, the term "compound" refers to a composition or mixture obtained by melt mixing or compounding a neat polymer and at least one other ingredient, including but not limited to one or more additives and/or one or more other polymers.
As used herein, "ΔE" refers to the perceived COLOR difference in the CIELAB COLOR space and under a D65 light source as measured according to ASTM E1347-6 using a COLOR EYE 7000A instrument available from Macbeth (X-Rite) Inc.
As used herein, "haze" is a measure of the loss of transparency measured according to ASTM D1003. Transparency can also be assessed qualitatively by visual inspection.
As used herein, the term "free" of a component or substance means that the amount of the component or substance is not present in an intentional addition, in some embodiments, the term means that a functionally effective amount of the component or substance is not present, and in other embodiments, the term means that the amount of the component or substance is not present.
As used herein, the term "molded from … …" in connection with articles (or article parts) and materials means that the articles (or article parts) are molded, extruded, shaped, formed, or otherwise made from the materials. Thus, in some embodiments, the term "molded from … …" means that the article (or article component) can comprise, consist essentially of, or consist of the material; also, in other embodiments, the article (or article component) is composed of a material, as the article (or article component) is made, for example, by an injection molding process.
As used herein, the term "QUV test" refers to an accelerated weathering test according to ASTM E1347-06, using the following equipment and conditions:
-device: QUV/spray accelerated weathering tester available from Q-Lab company;
UV irradiance: 0.68W/m 2 ；
-temperature: 45 ℃; and
duration of: 14 days.
As used herein, the term "visually observable" (including "visual observation" and other similar terms) refers to being observable (or made observable) by the naked eye at a distance of no more than 50 centimeters from the naked human eye under conventional indoor lighting conditions.
As used herein, the term "yellowing index" refers to the yellowing grade measured according to ASTM E313 using a COLOR EYE 7000A instrument purchased from Macbeth (X-Rite) company.
Thermoplastic polyurethane compound and molded article
Aspects of the invention relate to thermoplastic polyurethane compounds. Other aspects of the invention relate to thermoplastic articles molded from the thermoplastic polyurethane compounds.
According to the invention, the thermoplastic polyurethane compound comprises a blend of an aromatic polycaprolactone-type thermoplastic polyurethane and a further aromatic thermoplastic polyurethane selected from: aromatic polyester thermoplastic polyurethane, aromatic polyether thermoplastic polyurethane, and combinations thereof, wherein about 20 to about 99 parts by weight is an aromatic polycaprolactone thermoplastic polyurethane and about 1 to about 80 parts by weight is other aromatic thermoplastic polyurethane. In addition, the thermoplastic polyurethane compound is free of aliphatic polycaprolactone-type thermoplastic polyurethane. Thermoplastic articles molded therefrom achieve a rating of 2 or higher according to the blue jeans abrasion resistance test (Blue Jean Abrasion Test).
Surprisingly, it has been found that blue jeans stain resistance (resistance to Blue Jean Staining) of thermoplastic articles molded from thermoplastic polyurethane compounds can be improved when the thermoplastic polyurethane compounds include a blend selected from the group consisting of aromatic polycaprolactone-type thermoplastic polyurethanes and other aromatic thermoplastic polyurethanes selected from the group consisting of aromatic polyester-type thermoplastic polyurethanes, aromatic polyether-type thermoplastic polyurethanes, and combinations thereof.
In some embodiments, the thermoplastic polyurethane is selected from: aromatic polycaprolactone-type thermoplastic polyurethanes and other aromatic thermoplastic polyurethanes selected from: aromatic polyester-type thermoplastic polyurethanes, aromatic polyether-type thermoplastic materials, and combinations thereof, wherein about 60 to about 99 parts by weight is an aromatic polycaprolactone-type thermoplastic polyurethane, and about 1 to about 40 parts by weight is other aromatic thermoplastic polyurethane.
In some embodiments, the thermoplastic polyurethane compound further comprises an additive selected from the group consisting of: antioxidants and stabilizers; a colorant; a release agent; a processing aid; an ultraviolet absorber; and combinations thereof.
In some embodiments, the thermoplastic polyurethane compound further comprises a second polymer selected from the group consisting of: styrenic block copolymers, thermoplastic vulcanizates, polyolefin elastomers, copolyesters, and combinations thereof.
In some embodiments, the thermoplastic polyurethane compound further comprises a plasticizer.
In some embodiments, the thermoplastic polyurethane compound is free of aliphatic polyester thermoplastic polyurethane, aliphatic polyether thermoplastic material, and combinations thereof.
In some embodiments, the thermoplastic article achieves a Δe of about 7.5 to about 20 and a yellowness index of about 11.5 to 30 after being subjected to the QUV test.
Blends of aromatic thermoplastic polyurethanes
In general, thermoplastic Polyurethanes (TPU) include block copolymers composed of hard segments and soft segments. The hard segment is composed of the reaction of an isocyanate with a chain extender or short chain diol. The soft segment is formed by the reaction of an isocyanate with a polyol or a long chain diol. Based on the chemical nature of the isocyanate component, TPU can be divided into two categories: (1) aromatic; and (2) aliphatic. Additionally, TPU can be categorized into three categories based on the chemical nature of the soft segment: (1) polyester type; (2) polyether type; (3) polycaprolactone type.
According to the invention, the thermoplastic polyurethane compound comprises a blend of an aromatic polycaprolactone-type thermoplastic polyurethane and a further aromatic thermoplastic polyurethane selected from: aromatic polyester thermoplastic polyurethane, aromatic polyether thermoplastic polyurethane, and combinations thereof.
Suitable aromatic polycaprolactone type thermoplastic polyurethanes include conventional or commercially available aromatic polycaprolactone type thermoplastic polyurethanes. A single commercial grade aromatic polycaprolactone-type thermoplastic polyurethane or a combination of two or more different commercial grades of aromatic polycaprolactone-type thermoplastic polyurethane may be used as the aromatic polycaprolactone-type thermoplastic polyurethane in the disclosed invention.
Non-limiting examples of commercially available aromatic polycaprolactone-type thermoplastic polyurethanes include: those under the PEARLTHANE brand from Lubrizol, e.g., grade 11T85, those under the ESTANE brand from Lubrizol, e.g., grades 2102-90A and 2102-55D.
Suitable aromatic polyester thermoplastic polyurethanes include conventional or commercially available aromatic polyester thermoplastic polyurethanes. A single commercial grade aromatic polyester thermoplastic polyurethane or a combination of two or more different commercial grades of aromatic polyester thermoplastic polyurethane may be used as the aromatic polyester thermoplastic polyurethane in the disclosed invention.
Non-limiting examples of commercially available aromatic polyester thermoplastic polyurethanes include those available under the ELASTOLLA brand from Basf, inc., such as grade S85A 55N.
Suitable aromatic polyether thermoplastic polyurethanes include conventional or commercially available aromatic polyether thermoplastic polyurethanes. A single commercial grade aromatic polyether thermoplastic polyurethane or a combination of two or more different commercial grades of aromatic polyether thermoplastic polyurethane may be used as the aromatic polyether thermoplastic polyurethane in the disclosed invention.
Non-limiting examples of commercially available aromatic polyether thermoplastic polyurethanes include those available under the irgo gan brand from Huntsman (Huntsman), such as a 85p 43940 uv grade.
Optional additives
In some embodiments, the thermoplastic polyurethane compound further comprises one or more optional additives.
Suitable optional additives include conventional or commercially available plastics additives. Those skilled in the art of thermoplastic compounding can, without undue experimentation, select suitable additives from available references such as E.W.Flick, plastic design library (Plastics Design Library)Plastic additive database(Plastics Additives Database)》(Elsevier 2004)。
The optional additives may be used in any amount sufficient to provide the desired processing or performance characteristics to the thermoplastic polyurethane compound and/or the thermoplastic article molded therefrom. The amount should not result in waste of additives or adverse processing or performance of the thermoplastic polyurethane compound and/or thermoplastic articles molded therefrom.
Non-limiting examples of optional additives include: an adhesion promoter; an anti-fogging agent; an antioxidant; an antistatic agent; biocides (antibacterial, fungicidal and fungicidal agents); colorants, including pigments and dyes; a dispersing agent; fillers and extenders; fire retardants, flame retardants and smoke suppressants; a hardness regulator; an impact modifier; an initiator; a lubricant; mica; a release agent; an oil and a plasticizer; a processing aid; a second polymer; silanes, titanates and zirconates; a slip agent and an antiblocking agent; a stabilizer; stearate; an ultraviolet absorber; a viscosity modifier; and wax.
In some embodiments, the thermoplastic polyurethane compound further comprises one or more of the following: antioxidants and stabilizers; a colorant; a release agent; an ultraviolet absorber; and combinations thereof.
Optionally a second polymer
In some embodiments, the thermoplastic polyurethane compound further comprises a second polymer (i.e., a polymer resin that is different from the thermoplastic polyurethane component).
In thermoplastic polyurethane compounds, the second polymer should be compatible with the thermoplastic polyurethane and may, for example, be advantageous in improving processability or desired physical properties, such as hardness.
Suitable second polymers include thermoplastic elastomers other than thermoplastic polyurethanes, such as styrenic block copolymers, thermoplastic vulcanizates, polyolefin elastomers, copolyesters, and combinations thereof.
Non-limiting examples of suitable styrenic block copolymers include styrene-ethylene/butylene-styrene (SEBS), styrene-ethylene/propylene-styrene (SEPS), styrene-ethylene/propylene-styrene (SEEPS), styrene-isobutylene-styrene (SIBS), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), and combinations thereof.
Non-limiting examples of suitable thermoplastic vulcanizates (TPVs) include: blends of a continuous phase of polyolefin (e.g., polypropylene) and a discontinuous phase of vulcanized rubber (e.g., crosslinked EPDM).
Non-limiting examples of suitable polyolefin elastomers include: propylene-based elastomers, ethylene/alpha-olefin random copolymers, and combinations thereof.
Non-limiting examples of suitable copolyesters include block copolymers consisting of repeating soft segments of aliphatic polyethers or aliphatic polyesters and hard segments of aromatic polyesters.
Optional plasticizer
In some embodiments, particularly when a thermoplastic elastomer other than a thermoplastic polyurethane is included as the second polymer, the thermoplastic polyurethane compound also includes a plasticizer.
Plasticizers may be used, for example, to adjust softness and/or to improve flow properties or other properties of thermoplastic polyurethane compounds.
Any conventional oil (e.g., mineral oil, vegetable oil, synthetic oil, etc.) that plasticizes the styrenic block copolymer can be used in the present invention. Examples of commercially available oils include: PURETOL 380 brand oil available from Canadian Petroleum corporation (Petro-Canada); and PRIMOL 382 brand oil available from ExxonMobil.
Ranges of ingredients in TPE compounds
Table 1 below shows the ranges of ingredients in parts by weight that are acceptable, desirable, and preferred for some embodiments of the Thermoplastic Polyurethane (TPU) compounds of the disclosed invention. Other possible ranges of ingredients for other embodiments of the disclosed invention are described elsewhere herein.
In some embodiments, the thermoplastic polyurethane compound may comprise, consist essentially of, or consist of these components. Any numerical value between the end of the ranges is also considered an end of a range, so that all possible combinations are considered to be within the possible ranges shown in table 1 as embodiments of the compounds used in the disclosed invention. Unless explicitly stated otherwise herein, any disclosed numerical value means the exact disclosed numerical value as well as "about" the disclosed numerical value, such that any possibility is contemplated as some embodiments of the compounds used in the disclosed invention within the possibilities of table 1.
Processing and manufacturing method
Once the appropriate ingredients are selected, the preparation of the thermoplastic polyurethane compounds of the disclosed invention is not complex. The compounding may be carried out in a batch or continuous operation.
Mixing in a continuous process is typically carried out in an extruder, the temperature of which is raised to a level sufficient to melt the polymer matrix, and all of the additives are added at the feed throat, or by injection or side feeders downstream. The extruder speed may range from about 200 to about 700 revolutions per minute (rpm), for example from about 250 to about 350rpm. Typically, the output of the extruder is pelletized for later processing into thermoplastic articles.
Once the thermoplastic polyurethane compound of the present invention is provided, the subsequent preparation of the thermoplastic article of the disclosed invention is not complicated. For example, the thermoplastic articles of the present invention may be prepared by injection molding, extrusion, blow molding, rotational molding, thermoforming, calendaring, and the like.
Processing techniques are described in available references, for example, domiick V.Rosatoo et al, handbook of Plastic design (Plastics Design Handbook) (Springer) 2013.
In some embodiments, the thermoplastic elastomer compound of the disclosed invention is molded into a thermoplastic article by an injection molding process.
Other aspects of the invention relate to overmolded articles prepared by the overmolding process.
According to the invention, the overmolding preparation comprises: (a) An overmolded portion comprising a thermoplastic article of any embodiment of the disclosed invention; and (b) a substrate portion molded from the thermoplastic resin compound. The overmolded portion is bonded to the substrate portion at a bonding interface, and the bonding interface is free of adhesive. The thermoplastic resin compound comprises a thermoplastic resin and optionally additives. Non-limiting examples of suitable thermoplastic resins include: polyamides, polycarbonates (PC), acrylonitrile-butadiene-styrene (ABS), polycarbonate/acrylonitrile-butadiene-styrene (PC/ABS), styrene-acrylonitrile (SAN), and the like.
Method for improving blue jeans pollution resistance
Aspects of the present invention relate to methods of improving the resistance of thermoplastic articles molded from thermoplastic polyurethane compounds to blue jeans soiling. The method comprises the following steps: a blend of an aromatic polycaprolactone-type thermoplastic polyurethane and other aromatic thermoplastic polyurethane is selected, the other aromatic thermoplastic polyurethane being selected from: aromatic polyester thermoplastic polyurethane, aromatic polyether thermoplastic polyurethane, and combinations thereof,
wherein about 20 to about 99 parts by weight is an aromatic polycaprolactone-type thermoplastic polyurethane and about 1 to about 80 parts by weight is other aromatic thermoplastic polyurethane. In addition, the thermoplastic polyurethane compound is free of aliphatic polycaprolactone-type thermoplastic polyurethane. Thermoplastic articles molded therefrom achieve a rating of 2 or higher according to the blue jeans abrasion resistance test (Blue Jean Abrasion Test).
In some embodiments, the method comprises: thermoplastic polyurethane compounds of any of the embodiments of the disclosed invention are provided. In other embodiments, the method comprises: thermoplastic articles are molded from the thermoplastic polyurethane compound of any of the embodiments of the disclosed invention.
The utility of the invention
The thermoplastic polyurethane compounds of the disclosed invention can be used to prepare any type of thermoplastic article, or any thermoplastic part/component of a multi-part article or device, whose properties (e.g., such as enhanced abrasion and stain resistance and good clarity) are desirable or desired.
Thermoplastic polyurethane compounds of the disclosed invention have potential for various applications in a variety of different industrial fields, including but not limited to: automotive and transportation; a consumer product; an electronic device; health care and medical treatment; a household appliance; and other industrial fields or applications that benefit from the unique combination of properties of the compound.
In some embodiments, thermoplastic polyurethane compounds of the present invention from which protective cases for personal electronic devices, such as smart phones or other devices, can be made, users often put and remove garments or clothing made of jeans or other dyed fabrics (e.g., pockets of blue jeans).
Aspects of the invention relate to electronic devices comprising the thermoplastic articles described herein.
Other aspects of the invention relate to an accessory for an electronic device, wherein the accessory comprises a thermoplastic article as described herein. In some embodiments, the accessory is a protective case for a handheld electronic device.
Examples
Non-limiting examples of thermoplastic polyurethane compounds of various embodiments of the disclosed invention are provided.
Table 2 below identifies the components of the thermoplastic polyurethane compounds of the examples and their sources.
To prepare the examples, all ingredients were compounded together on a twin screw extruder and extruded into pellets at 196℃at 300 rpm. Subsequently, the extruded pellets were injection molded (barrel temperature 205 ℃ C. And mold temperature (molder temperature) 25 ℃ C.) into sample plates of size 150x125x1.5mm, and the recorded properties were evaluated.
Table 3 below shows the formulations and certain properties of comparative examples A-D.
Table 4 below shows the formulation and certain properties of comparative examples A-C.
Those of ordinary skill in the art, with no undue experimentation, can make and use the various aspects of the disclosed invention with the specification, including the examples.
All documents referred to in the embodiments of the present invention are incorporated herein by reference in their entirety unless otherwise indicated. Citation of any document is not an admission that it is prior art with respect to the disclosed invention.
While particular embodiments of the disclosed invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is intended that the appended claims cover all such changes and modifications that are within the scope of the disclosed invention.
Claims (15)
1. Use of a thermoplastic polyurethane compound for improving the stain resistance of a thermoplastic article against blue jeans, said thermoplastic polyurethane compound comprising:
100 parts by weight of a thermoplastic polyurethane selected from: blends of aromatic polycaprolactone-type thermoplastic polyurethane and other aromatic thermoplastic polyurethane selected from: aromatic polyester-type thermoplastic polyurethane, aromatic polyether-type thermoplastic polyurethane, and combinations thereof, wherein 20 to 99 parts by weight is aromatic polycaprolactone-type thermoplastic polyurethane, and 1 to 80 parts by weight is other aromatic thermoplastic polyurethane;
wherein the thermoplastic polyurethane compound is free of aliphatic polycaprolactone-type thermoplastic polyurethane; and is also provided with
According to the blue jeans abrasion resistance test, the thermoplastic article reaches a grade 2 or higher,
thermoplastic articles are accessories for electronic devices.
2. Use according to claim 1, wherein 60 to 99 parts by weight are aromatic polycaprolactone type thermoplastic polyurethanes and 1 to 40 parts by weight are other aromatic thermoplastic polyurethanes.
3. Use according to claim 1 or 2, wherein the thermoplastic polyurethane compound further comprises a processing aid.
4. The use according to claim 3, wherein the processing aid is selected from stabilizers; a colorant; a release agent; and combinations thereof.
5. The method according to claim 4, wherein the stabilizer is selected from the group consisting of antioxidants and ultraviolet absorbers.
6. Use according to claim 1 or 2, wherein the thermoplastic polyurethane compound further comprises a second polymer selected from the group consisting of: styrenic block copolymers, thermoplastic vulcanizates, polyolefin elastomers, copolyesters, and combinations thereof.
7. Use according to claim 1 or 2, wherein the thermoplastic polyurethane compound further comprises a plasticizer.
8. Use according to claim 1 or 2, wherein the thermoplastic polyurethane compound is free of aliphatic polyester thermoplastic polyurethane and aliphatic polyether thermoplastic polyurethane.
9. Use according to claim 1 or 2, wherein the thermoplastic article, after being subjected to the QUV test, attains a Δe of 7.5 to 20 and a yellowing index of 11.5 to 30.
10. Use according to claim 1 or 2, wherein the accessory is a protective case for a handheld electronic device.
11. Use according to claim 1 or 2, wherein the thermoplastic article is an overmolded article comprising:
(a) An overmolded portion comprising the thermoplastic article of any of claims 1-9; and
(b) A substrate portion molded from a thermoplastic resin compound;
wherein the overmolded portion is bonded to the substrate portion at a bonding interface, and the bonding interface is free of adhesive.
12. A method for improving blue jean stain resistance for a thermoplastic article molded from a thermoplastic polyurethane compound comprising 100 parts by weight of a thermoplastic polyurethane, said method comprising the steps of:
the thermoplastic polyurethane is selected from: aromatic polycaprolactone-type thermoplastic polyurethanes and other aromatic thermoplastic polyurethanes selected from: aromatic polyester-type thermoplastic polyurethane, aromatic polyether-type thermoplastic polyurethane, and combinations thereof, wherein 20 to 99 parts by weight is aromatic polycaprolactone-type thermoplastic polyurethane, and 1 to 80 parts by weight is other aromatic thermoplastic polyurethane;
wherein the thermoplastic polyurethane compound is free of aliphatic polycaprolactone-type thermoplastic polyurethane; and is also provided with
According to the blue jeans abrasion resistance test, the thermoplastic article reaches a grade 2 or higher,
thermoplastic articles are accessories for electronic devices.
13. The method of claim 12, wherein 60 to 99 parts by weight is an aromatic polycaprolactone-type thermoplastic polyurethane and 1 to 40 parts by weight is other aromatic thermoplastic polyurethane.
14. The method of claim 12 or claim 13, wherein the thermoplastic polyurethane compound is free of aliphatic polyester thermoplastic polyurethane and aliphatic polyether thermoplastic polyurethane.
15. The method of claim 12 or 13, wherein the thermoplastic article is a protective case or a portion thereof for a handheld electronic device.
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| US62/790,311 | 2019-01-09 | ||
| PCT/US2020/012481 WO2020146311A1 (en) | 2019-01-09 | 2020-01-07 | Thermoplastic polyurethane compounds exhibiting enhanced stain resistance |
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| CN113272384B true CN113272384B (en) | 2024-02-13 |
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| US (1) | US20220081561A1 (en) |
| EP (1) | EP3908629A4 (en) |
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Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5028658A (en) * | 1989-09-18 | 1991-07-02 | Monsanto Company | Sheet of polyvinyl butyral and polyurethane |
| WO1995013307A1 (en) * | 1993-11-12 | 1995-05-18 | Refac International, Ltd. | Polymer viscosity depressant/super cooling thermoplastic urethane |
| US5516857A (en) * | 1993-06-25 | 1996-05-14 | Refac International, Ltd. | Thermoplastic urethane elastomeric alloys |
| JP2000319502A (en) * | 1999-05-14 | 2000-11-21 | Hokushin Ind Inc | Polyesterurethane composition |
| US6342047B1 (en) * | 1998-06-02 | 2002-01-29 | Terumo Kabushiki Kaisha | Indwelling catheter |
| CA2419324A1 (en) * | 2002-02-18 | 2003-08-18 | Carl Freudenberg Kg | Thermoplastically processable polyurethane molding compound |
| CN1662605A (en) * | 2002-06-17 | 2005-08-31 | 诺沃恩Ip控股公司 | Reactive blend polymer compositions with thermoplastic polyurethane |
| CN101277990A (en) * | 2005-09-30 | 2008-10-01 | 陶氏环球技术公司 | Thermoplastic polyurethane containing structural units of polyester and polyether diols |
| EP2377898A1 (en) * | 2010-04-13 | 2011-10-19 | Evonik Degussa GmbH | Processing aid for thermoplastic polyurethanes |
| CN104936764A (en) * | 2012-12-03 | 2015-09-23 | 德莎欧洲公司 | Lamination made of rigid substrates with thin adhesive strips |
| CN106103527A (en) * | 2014-01-17 | 2016-11-09 | 路博润先进材料公司 | Selective laser sintering and system use method and its goods of thermoplastic polyurethane |
| CN106795369A (en) * | 2014-08-12 | 2017-05-31 | 玛尔提贝斯股份有限公司 | Thermoplastic polyurethane elastomer silicone |
| CN107129674A (en) * | 2016-02-29 | 2017-09-05 | 万华化学集团股份有限公司 | A kind of thermoplastic polyurethane composite of low-luster and its preparation method and application |
| WO2018029131A1 (en) * | 2016-08-09 | 2018-02-15 | Solvay Specialty Polymers Italy S.P.A. | Porous membranes |
| CN108003602A (en) * | 2017-11-09 | 2018-05-08 | 河北邦泰氨纶科技有限公司 | Cable, cable jacket Thermoplastic polyurethane composite material and preparation method thereof |
| CN108017900A (en) * | 2017-12-22 | 2018-05-11 | 广州机械科学研究院有限公司 | A kind of hydropneumatic sealing self-lubricating thermoplastic polyurethane elastomer material and its preparation method and application |
| CN108084392A (en) * | 2017-11-09 | 2018-05-29 | 河北邦泰氨纶科技有限公司 | High diathermanous plastic polyurethane of mobile phone protective cover and preparation method thereof |
| CN108456416A (en) * | 2017-02-21 | 2018-08-28 | 万华化学集团股份有限公司 | A kind of composition for thermoplastic elastomer and preparation method thereof for the encapsulated nylon of low temperature |
| WO2018164235A1 (en) * | 2017-03-08 | 2018-09-13 | テルモ株式会社 | Indwelling catheter |
| WO2018200510A1 (en) * | 2017-04-28 | 2018-11-01 | Polyone Corporation | Damping thermoplastic elastomer blends exhibiting clarity |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100160545A1 (en) * | 2006-10-05 | 2010-06-24 | Charles Page | Thermoplastic elastomers of styrenic block copolymers and aliphatic thermoplastic polyurethanes |
-
2020
- 2020-01-07 WO PCT/US2020/012481 patent/WO2020146311A1/en unknown
- 2020-01-07 EP EP20737919.9A patent/EP3908629A4/en active Pending
- 2020-01-07 US US17/420,849 patent/US20220081561A1/en active Pending
- 2020-01-07 CN CN202080008301.2A patent/CN113272384B/en active Active
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5028658A (en) * | 1989-09-18 | 1991-07-02 | Monsanto Company | Sheet of polyvinyl butyral and polyurethane |
| US5516857A (en) * | 1993-06-25 | 1996-05-14 | Refac International, Ltd. | Thermoplastic urethane elastomeric alloys |
| WO1995013307A1 (en) * | 1993-11-12 | 1995-05-18 | Refac International, Ltd. | Polymer viscosity depressant/super cooling thermoplastic urethane |
| US6342047B1 (en) * | 1998-06-02 | 2002-01-29 | Terumo Kabushiki Kaisha | Indwelling catheter |
| JP2000319502A (en) * | 1999-05-14 | 2000-11-21 | Hokushin Ind Inc | Polyesterurethane composition |
| CA2419324A1 (en) * | 2002-02-18 | 2003-08-18 | Carl Freudenberg Kg | Thermoplastically processable polyurethane molding compound |
| CN1662605A (en) * | 2002-06-17 | 2005-08-31 | 诺沃恩Ip控股公司 | Reactive blend polymer compositions with thermoplastic polyurethane |
| CN101277990A (en) * | 2005-09-30 | 2008-10-01 | 陶氏环球技术公司 | Thermoplastic polyurethane containing structural units of polyester and polyether diols |
| EP2377898A1 (en) * | 2010-04-13 | 2011-10-19 | Evonik Degussa GmbH | Processing aid for thermoplastic polyurethanes |
| CN104936764A (en) * | 2012-12-03 | 2015-09-23 | 德莎欧洲公司 | Lamination made of rigid substrates with thin adhesive strips |
| CN106103527A (en) * | 2014-01-17 | 2016-11-09 | 路博润先进材料公司 | Selective laser sintering and system use method and its goods of thermoplastic polyurethane |
| CN106795369A (en) * | 2014-08-12 | 2017-05-31 | 玛尔提贝斯股份有限公司 | Thermoplastic polyurethane elastomer silicone |
| CN107129674A (en) * | 2016-02-29 | 2017-09-05 | 万华化学集团股份有限公司 | A kind of thermoplastic polyurethane composite of low-luster and its preparation method and application |
| WO2018029131A1 (en) * | 2016-08-09 | 2018-02-15 | Solvay Specialty Polymers Italy S.P.A. | Porous membranes |
| CN108456416A (en) * | 2017-02-21 | 2018-08-28 | 万华化学集团股份有限公司 | A kind of composition for thermoplastic elastomer and preparation method thereof for the encapsulated nylon of low temperature |
| WO2018164235A1 (en) * | 2017-03-08 | 2018-09-13 | テルモ株式会社 | Indwelling catheter |
| WO2018200510A1 (en) * | 2017-04-28 | 2018-11-01 | Polyone Corporation | Damping thermoplastic elastomer blends exhibiting clarity |
| CN108003602A (en) * | 2017-11-09 | 2018-05-08 | 河北邦泰氨纶科技有限公司 | Cable, cable jacket Thermoplastic polyurethane composite material and preparation method thereof |
| CN108084392A (en) * | 2017-11-09 | 2018-05-29 | 河北邦泰氨纶科技有限公司 | High diathermanous plastic polyurethane of mobile phone protective cover and preparation method thereof |
| CN108017900A (en) * | 2017-12-22 | 2018-05-11 | 广州机械科学研究院有限公司 | A kind of hydropneumatic sealing self-lubricating thermoplastic polyurethane elastomer material and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| Assessment of the chemical risk factor for application of artificial cardiac pacemakers equipped with a head made of thermoplastic polyurethane compound;Lanina, S.Y等;Inorganic Materials: Applied Research;第7卷(第5期);第737-744页 * |
| PCL型热塑性聚氨酯的合成及性能研究;刘洋子健等;《化工新型材料》;20181015(第10期);第159-161+166页 * |
| 杨东武等.第65页.《塑料材料选用技术》.中国轻工业出版社,2008, * |
| 许健南.《塑料材料》.《塑料材料》.1991,第324-325页. * |
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| WO2020146311A1 (en) | 2020-07-16 |
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| US20220081561A1 (en) | 2022-03-17 |
| CN113272384A (en) | 2021-08-17 |
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